Azo compounds of the anthraquinone series



Patented Feb. 1%, 1953 AZO COMPOUNDS OF THE ANTHRAQUINONE SERIES Frederic B. Stilmar, Wilmington, BeL, assignor to I E. ll. du Pontde Nemours & Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application March 15, 1949, Serial No. 81,616

5 Claims.

This invention relates to the preparation of a new class of compounds of the anthraquinone series, and more particularly new acylated 1- aminoand l-nitroanthraa inone-Z-carbonyl hydrazines.

The anthraquincne vat dyes are known to be of particular value because of their excellent fastness properties, and, while a large range of colors has been produced commercially, there has not been produced a red dye in this class which will dye in the bright shades desirable and have the good fastness properties of dyes of this class in general. Severalred dyes have been produced in the anthraquinone series, but they lack the strength or brightness or certain fastness properties which are particularly desirable and which usually identify the dyes of this class.

It is an object of the present invention to produce a class of new compounds which, although exhibiting dye properties in themselves, are particularly useful as intermediates in the preparation of bright red dyes of the anthraquinonc vat dye class which exhibit excellent fastness properties and high tinctorial strength. A more specific object of the invention is to produce acylated 1-aminoand l-nitroanthraquinone-Z- carbonyl hydrazines from organic dicarboxylic acid chlorides of the formula:

in which R stands for a hydrocarbon radical of the group consisting of benzene and diphenyl radicals and X for a connecting bridge of the group consisting of -N=N, CH=CI-l-, CII2, O--, S-, -SO2- and CO.

The compounds of this invention are prepared by reacting 1-aminoanthraquinone-2-carbonylhydrazine or 1-nitroanthraquinone-2-carbonylhydrazine with an acid chloride of an aromatic dicarboxylic acid containing at least two phenyl groups connected through C- 0-, -S or -N-, such as azo-benzene-dicarbonyl chlorides, azo-diphenyl-dicarbonyl chlorides, stilbene-dicarbonyl chlorides, diphenylmethanedicarbonyl chlorides, diphenylsulfide-dicarbonyl chlorides, diphenyl-ether-dicarbonyl chlorides, diphenylsulfone-dicarbonyl chlorides and benzephenone-dicarbonyl chlorides, which types of dicarbonyl chlorides are illustrated in the following examples. The reaction of the hydrazine and the dicarbonyl chloride is preferably carried out at elevated temperatures in an inert solvent such as nitrobenzene or trichlorobenzene. excellent yields of the acylated hydrazines are obtained which have the general formula:

- oxdiazole rings is efiected. These dyes are more particularly disclosed and claimed in co-pending application Serial No. 81,617 filed March 15, 1949.

The following examples are given to illustrate the invention. The parts used are by weight, unless otherwise specified.

Example 1 8.5 parts of azobenzenelA-dicarbonyl chloride, 20 parts of lnitroanthraquinone-2-carbonyl hydrazine and 200 parts of nitrobenzene are mixed under agitation and slowly heated to 175 C. This temperature is maintained for one hour. The product, in the form of light yellow needles, is filtered off, washed with benzene and dried.

This product has a melting point of 289-291 C. and dyes cotton in weak red shades from a yellowish-red alkaline hydrosulfite vat (with reduction of the nitro groups to the amine). The dyeing changes to a dull violet color with alkali. It dissolves in sulfuric acid, giving a yellow color, and has the formula:

2,628,231 3 4 Example 2 tion occurs (with the formation of the diacid chloride).

The excess thionyl chloride is removed by blowing with a stream of air and there is then added 5 13.2 parts of 1-nitroanthraquinone-2-carbonyl hydrazine.

After heating the mass under agitation at 160-165 C. for 8 hours, the resulting product is filtered off, washed with benzene and dried. The

10 product has the formula:

A mixture of 92.2 parts of azobiphenyl-4,4- dicarbonyl chloride, 13.7 parts of l-nitroanthraquinone-Z-carbonyl hydrazine and 200 parts of nitrobenzene is slowly heated to 175l80 C. and agitated for three hours at that temperature. The product, which precipitates as yellow plates, is filtered off, washed with benzene and dried. This product vats with reduction of the nitro groups to the amines, and dyes cotton orange O l H shades that turn bluer when treated with alkali. Emmple 5 It has the formula: A mixture of 1.7 parts of diphenylsulfone-4A- 0 N02 N02 0 1 I| lHl|\lH NH-NH u -o N=N 11 O0 0Q 11 u 0 o Example 3 dicarbonyl chloride, 100 parts of ortho-dichlorobenzene and 3.4 parts of l-nitroanthraquinone- Z-carbonyl hydrazine is heated slowly to 160- 170 C. and held for two hours with stirring. The product precipitates as small colorless crystals and is filtered off, washed with benzene and dried.

It dyes cotton from a red-colored alkaline hydrosulfite vat. The dyeing is a weak red turning violet when treated with alkali. Its sulfuric acid solution is almost colorless. The formula of this product is considered to be:

A mixture of 4.6 parts of azobiphenyl-4,4'- dicarbonyl chloride, 6.7 parts of l-aminoanthraquinone-Z-carbonyl hydrazine and 150 parts of nitrobenzene is slowly heated to 170 C. and agitated for 10 hours at this temperature. The resulting product, consisting of very fine orange particles, is filtered off and washed with benzene and dried. It dyes cotton in scarlet-orange shades 40 from a red alkaline hydrosulfite vat. When treated with free alkali, the dyeings become wine- 0 N03 N05 0 I E a-Em (g) $114213 u t t O l O l l violet. The color in sulfuric acid is reddish-yel- Example; low. It has the formula: 1 part of benzophenone-4,4'-dicarbony1, chlo- Example 4 ride, 2 parts of 1-nitroanthraquinone-2-carbonyl hydrazine, and 35 parts of ortho-dichlorobenzene A mixture of 5 parts of diphenylether-4,l'- are mixed under agitation and the mixture is dicarboxylic acid, 150 parts of nitrobenzene, 10 heated at 160-170 C. for two hours. The colorparts of thionyl chloride and part of pyridine less intermediate is isolated as in the above exis heated at 100-110 C. under reflux until soluamples. It has the formula:

5 Emmpze 7 solvent in which it is formed, although where preferred it may be first prepared in any desired 6.1 parts of azobenzene-3,3-dicarbonyl chlomanner and after isolation condensed with the ride, 13.6 parts of 1-nitroanthraquinone-2-caranthraquinone-2-carbonyl hydrazine. It will be bonyl hydrazine, and 260 parts of ortho-dichloro- 5 obvious that other acid halides can be employed benzene are mixed and, while agitated, the mixin place of the acid chloride. ture is heated to 160-1'70 C. and maintained for By vatting the nitro compounds produced from two hours. The pale yellowish bis-hydrazide the l-nitro-anthraquinone-Z-carbonyl hydrazine separates as very small micrccrystalline particles, with sodium hydrosulfite and caustic, they may be which is filtered oif, washed with benzene and 1 converted to the corresponding amino compounds. dried. It has the formula: Usually, however, it will be found desirable to 0 N02 N=N No, 0 Iii-EEG 23 t t t t Diphenylmethane-3,3-dicarbony1 chloride, (11- effect ring closure of the nitro compounds prior phenylsulfide-4,4-dicarbony1 chloride or stilto their reduction to the amines. bene-4,4'-dicarbony1 chloride may be substituted I claim: for the particular dicarbonyl chlorides employed 25 1. The acylated anthraquinone-carbonyl hyin the above examples to give new acylated andrazines which have the general formula: thraquinone-Z-carbonyl hydrazines of similar re- 0 Y Y 0 activity and chemical properties. These com- H NENH NH NH pounds, as well as those specifically described in the examples, are all readily converted to the bis- 39 H g anthraquinone-oxdiazoles which are valuable 0 0 bright red-to-scarlet vat dyes.

The compounds of this invention may be ring g closed without isolation from the nitrobenzene or other solvent mass by adding the acid condensing 3 wherein R stands for a hydrocarbon radical of the agent such as thionyl chloride and continuing group consisting of benzene and diphenyl radicals, the heating at temperatures of from 160-170 C. and Y stands fOr a substituent of the group conto produce the oxdiazoles as more particularly sisting of -NH;; and -NO2.

disclosed in my co-pending application Serial No. 2. The acylated 1-nitroanthraquinone-Z-car- 81,617 filed March 15, 1949. bonyl hydrazine having the formula:

O NO: NO: 0 II NH--NH NH-NH I H As illustrated in the above examples, the di- 3. The acylated 1-aminoanthraquinone-2-carcarboxylic acid chloride may be formed as a prebonyl hydrazine having the formula:

0 NE: NH; 0 I m-NH NH-I|\IH u o -N=N- & o H II H H 0 o 0 o liminary step in the preparation of the conden- 4. The acylated l-nitroanthraquinone-Z-carsation product without isolation from the organic bonyl hydrazine having the formula:

NO 0 NH-NH 2,628,231 7 5. The eoylated l-vnitroanth'raquinone-z -carbonyl hydrazine having the formula:

FREDERIC B. STILMAR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,175,803 Honold et a1 Oct. 10, 1939 2,228,455 Honold et a1 Jan. 14, 1941 2,395,229 Lowe et a1 Feb. 19, 1946 2,567,132 Stilmar Sept. 4, 1951 

1. THE ACYLATED ANTHRAQUINONE-CARBONYL HYDRAZINES WHICH HAVE THE GENERAL FORMULA: 